WO2000006668A1 - Procede de traitement de composes organiques contenant du chlore - Google Patents

Procede de traitement de composes organiques contenant du chlore Download PDF

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Publication number
WO2000006668A1
WO2000006668A1 PCT/JP1999/004052 JP9904052W WO0006668A1 WO 2000006668 A1 WO2000006668 A1 WO 2000006668A1 JP 9904052 W JP9904052 W JP 9904052W WO 0006668 A1 WO0006668 A1 WO 0006668A1
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WO
WIPO (PCT)
Prior art keywords
chlorine
coal
waste plastics
ammonia
coke oven
Prior art date
Application number
PCT/JP1999/004052
Other languages
English (en)
Inventor
Ikuo Komaki
Hiroshi Uematsu
Kenji Kato
Original Assignee
Nippon Steel Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Steel Corporation filed Critical Nippon Steel Corporation
Priority to AU49291/99A priority Critical patent/AU4929199A/en
Priority to CA002338611A priority patent/CA2338611C/fr
Priority to US09/744,631 priority patent/US6329496B1/en
Priority to DE69930519T priority patent/DE69930519T2/de
Priority to EP99933136A priority patent/EP1114123B1/fr
Publication of WO2000006668A1 publication Critical patent/WO2000006668A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics

Definitions

  • chlorine-containing resins such as polyvinyl chloride and polyvinylidene chloride
  • chlorine-containing organic compounds such as polychlorinated biphenyls
  • resins such as polypropylene, polyethylene and polystyrene (the so-called 3Ps)
  • 3Ps resins such as polypropylene, polyethylene and polystyrene
  • the present invention relates to a processing method for recycling such waste plastics, particularly to a processing method recycling of chlorine-containing resins, chlorine-containing organic compounds or waste plastics containing these (chlorine-containing waste plastics) that is free of problems such as corrosion of processing equipment and degradation of product quality.
  • waste plastics After being used as plastic products, polyvinyl chloride, polyvinylidene chloride and other chlorine- containing resins and the like are discarded along with other plastic products without being sorted out. Waste plastics therefore inevitably include a chlorine component carried in by chlorine-containing resins and the like. Sorted waste plastics recovered from households do in fact ordinarily contain polyvinyl chloride and polyvinylidene chloride, which, when calculated as chlorine, contain several wt% of chlorine. When thermally decomposed at high temperatures, polyvinyl chloride and other chlorine- containing resins generate chlorine-type gases such as hydrogen chloride gas and chlorine gas.
  • waste plastics discarded as industrial waste and nonindustrial waste include so-called chlorine- containing resins, such as polyvinyl chloride and polyvinylidene chloride, and so-called chlorine-containing organic compounds such as polychlorinated biphenyls .
  • Waste plastics both industrial and nonindustrial, therefore on average include chlorine at about several wt% to several tens of wt% and, even after sorting, include chlorine at an average of several wt%.
  • chlorine-type gases such as chlorine and hydrogen chloride are generated during thermal decomposition of the waste plastics, causing a problem of corrosion of the shell, stave coolers and the like of the blast furnace body and a problem of corrosion of furnace-top waste gas equipment and the furnace-top electrical equipment.
  • preprocessing such as in advance sorting out and removing chlorine-containing resins, chlorine-containing organic compounds and other chlorine-containing waste plastics or removing only the chlorine component of the waste plastics, and the waste plastics have been charged in the blast furnace after having their chlorine content reduced to 0.5wt% or below.
  • waste plastics which are also hydrocarbons, are charged into the coke oven to obtain coke, tar, light oil and fuel gas by dry distillation.
  • a coke oven can thus also be used as a waste plastic recycling facility.
  • the amount of waste plastics charged into the coke oven is expected to be 10kg per ton of coal, because the coke quality deteriorates sharply when the waste plastic charging amount exceeds 10kg per ton of coal.
  • Waste plastics that have been collected from throughout a city and subjected to magnetic sorting, aluminum sorting etc. ordinarily contain a chlorine component of approximate from 3wt% to 5wt%. This is because the collected waste plastics contain from 6wt% to 10wt% of chlorine-containing waste plastics, mainly polyvinyl chloride and the like.
  • a blast furnace it is generally accepted that a problem of corrosion by the chlorine-type gases in the blast furnace will arise unless the ordinary chlorine content is lowered to 0.5wt% or below.
  • the waste plastics is charged into the coke oven after first lowering the chlorine content thereof to 0.5wt% or below.
  • the method for lowering the chlorine content of the waste plastics to 0.5wt% or below there is adopted either the method, using a dechlorinator, of thermally decomposing the waste plastics by heating to around 300°C and removing the chlorine component thereof as chlorine- type gases, or the method of separating the waste plastics into light plastics and heavy plastics by specific gravity separation using a centrifuge or the like and sorting out and selecting only the light plastics of low chlorine content.
  • the former method using a dechlorinator is very complicated because it is applied to all of the collected waste plastics.
  • the later method of separating into light plastics and heavy plastics by specific gravity separation using a centrifuge or the like and sorting out and selecting only the light plastics of low chlorine content is rather more generally adopted.
  • the specific gravity separation method also involves problems such as the following. Explanation will be made taking the method of specific gravity separation using a centrifuge as an example.
  • waste plastics of a chlorine content of 9.5-15.5wt% separated as heavy plastics are impossible to lower to a chlorine content of 0.5wt% by further dechlorination, they can only be treated as a residual to be disposed of as, for instance, landfill.
  • Treating them as residual involves processing costs and, what is more, this treatment is essentially indicative of the low recycle rate of the waste plastic recycle-processing method and cannot be called a practical recycle-processing method that responds to social requirements .
  • the present invention which is aimed at overcoming the foregoing technical problems, provides a processing method for recycling waste plastics that is capable of reducing or eliminating the load on the waste plastic dechlorination process heretofore considered indispensable in a processing method for recycling waste plastics containing 0.5wt% or more of chlorine and that has no problem of equipment corrosion or problem of product quality degradation.
  • the gist thereof is as set out below.
  • a method for processing chlorine-containing resin, chlorine-containing organic compound, or waste plastic containing the same characterized in thermally decomposing chlorine-containing resin, chlorine-containing organic compound or waste plastic containing the same, contacting generated thermal decomposition gas including chlorine-type gas with ammonia-containing gas or liquid, to take a chlorine component of the thermal decomposition gas into water as ammonium chloride, and further adding a strong base to the water containing the chlorine content to make the chlorine component into a strong basic salt.
  • a method for processing chlorine-containing resin, chlorine-containing organic compound, or waste plastic containing the same according to any of (l)-(5) above, characterized in that the chlorine-containing resin, chlorine-containing organic compound, or waste plastic containing the same is thermally decomposed in some coke oven chambers of a coke oven having multiple coke oven chambers, generated thermal decomposition gas including chlorine-type gas is contacted with ammonia liquor circulating through the coke oven, and chlorine component of the thermal decomposition gas is taken into the ammonia liquor as ammonium chloride.
  • a method for processing chlorine-containing resin, chlorine-containing organic compound, or waste plastic containing the same characterized in that chlorine- containing resin, chlorine-containing organic compound or waste plastic containing the same is thermally decomposed, ammonia generated during dry distillation of coal is used to take generated chlorine-type gas into ammonia liquor as ammonium chloride, and an amount of the coal used is that discharges ammonia at 1.1 to 2 times the molar amount of chlorine in the generated chlorine-type gas.
  • FIG. 1 is a flow diagram showing the present invention.
  • FIG. 2 is a schematic sectional view showing a state inside a coke oven of the present invention.
  • FIG. 3 is a diagram showing relationship between amount of added waste plastics and coke strength.
  • FIG. 4 is a diagram showing the chlorine concentrations of coke oven charge materials when waste plastics were added.
  • FIG. 5 is a diagram showing the distribution of chlorine in the raw material to the products when waste plastics were added.
  • FIG. 6 is a diagram showing the distribution of chlorine in the waste plastics to the products.
  • FIG. 7 is a diagram showing relationship between chlorine concentration in waste plastics and chlorine concentration in light oil.
  • FIG. 8 is a diagram showing relationship between chlorine concentration in waste plastics and chlorine concentration in tar.
  • FIG. 9 is a diagram showing a comparison of the porosity and the bulk density of silica brick before and after testing.
  • FIG. 10 is a diagram showing chlorine concentration of ammonia liquor when waste plastics containing chlorine were added to coal .
  • FIG. 11 is a diagram showing total nitrogen concentration of ammonia liquor after ammonia removal when waste plastics containing chlorine were added to coal.
  • FIG. 12 is a diagram showing relationship between caustic soda addition rate and conversion rate of fixed ammonia to free ammonia.
  • FIG. 13 is a diagram showing a caustic soda addition point.
  • FIG. 14 is a diagram showing effect of waste plastic addition/nonaddition on coke productivity.
  • FIG. 15 is a diagram showing a comparison of charged coal amount scatter with and without waste plastic addition.
  • FIG. 16 is a diagram showing a comparison of gas pressure in coal with and without waste plastic addition.
  • FIG. 17 is a diagram showing a comparison of amount of carbon deposit to the top portion of a coke oven chamber with and without waste plastic addition.
  • Coke-oven gas is generally generated when coal is dry distilled (carbonized) in the coke oven chambers of a coke oven. This gas includes a tar component, ammonia, water and so forth. After being discharged from the coke oven, this coke-oven gas is cooled by flushing with ammonia liquor (aqueous ammonia produced from the coal, stored and circulated as a coolant) and separated into coke-oven gas, tar, and ammonia liquor. The coke-oven gas is used as fuel gas and the ammonia liquor is circulated for use in flushing.
  • ammonia liquor aqueous ammonia produced from the coal, stored and circulated as a coolant
  • the present inventors comminuted waste plastics containing chlorine-system resins to about 10mm and volume-reduced them using a screw kneader.
  • the volume- reduction temperature was about 120°C owing to screw friction heating.
  • the properties of the volume-reduced waste plastics are shown in Table 2 and Table 3. What was obtained by cutting these to a diameter of about 10mm and air-cooling them on a conveyor belt was mixed in advance with coal at l-2wt% and charged into the coke oven chambers of a coke oven battery having 100 coke oven chambers.
  • the coke oven measured 430mm in width and 6.5m in height. Charging into the coke oven was from the top of the coke oven by the same method as for conventional coal charging.
  • the dry distillation pattern adopted was the same as that for conventional coke production.
  • the total dry distillation time was 20hr.
  • Coke-oven gas (hereinafter denoted as COG) generated during dry distillation contains ammonia and the COG is cooled by flushing ammonia liquor in the ascension pipes.
  • the ammonia liquor was added with caustic soda in accordance with its ammonium chloride concentration to convert the ammonium chloride to sodium chloride and ammonia, whereafter the ammonia was vaporized and removed in an ammonia remover.
  • the chlorine- type gases that becomes a problem in recycle-processing of waste plastics containing 0.5wt% or more of chlorine were made harmless as ammonium chloride and other chlorides.
  • the present inventors used the following method to investigate the percentage of chlorine input to the coke oven that distributed to the products.
  • Chlorine-containing waste plastics containing from 2.00wt% to 2.32wt% of chlorine were blended with coal at a blending rate of 1- 2wt% and the blend was dry distilled in a coke oven.
  • the coke, ammonia liquor and COG were sampled and the chlorine concentration of each product was measured.
  • the measurement of chlorine concentration was done by using ion chromatography to measure the Cl ion quantity of the chlorides obtained in accordance with the Testing Method for Cl by the Bomb Combustion Method of JIS K 2541 "Testing Method for Sulfur Component of Petroleum and Petroleum Products" and converting to total Cl amount.
  • Table 1 shows chlorine concentration of the products when chlorine-containing waste plastics containing 2.00wt% of chlorine were blended with coal at a blending rate of lwt% and the blend was dry distilled in a coke oven.
  • the present inventors further blended the waste plastics A (chlorine content: 2.32%) and the waste plastics B (chlorine content: 2.19%), whose compositions are shown in Table 2 and Table 3 , with coal at a blending rate of l-2wt%, dry distilled the blend in a coke oven, and measured the chlorine concentration of the products at this time. Since different types of coal were used in the respective tests for coal only and tests for coal added with waste plastics in Tables 1-3, the volatile components, alkali metals alkaline earth metals, and the like of the raw material coals differ somewhat.
  • FIG. 4 The coals containing these waste plastics were dry distilled in a coke oven and the chlorine concentration of the products were investigated. The results are shown in FIG. 5. The distribution ratio of chlorine from the waste plastics to the products was investigated. As shown in
  • FIG. 6 the results were 89% to ammonia liquor, 7% to coke and 4% to COG. Table 2
  • the present inventors investigated the effect on byproducts. As a result, as shown in FIGs. 7 and 8, it was ascertained that the chlorine concentrations of the light oil and the tar did not exceed the upper operational limits, i.e., that there was no problem.
  • the present inventors investigated effect on the silica brick of the coke oven by analyzing the porosity and bulk density of silica brick before and after two- month tests using waste plastics A and B. As a result, as shown in FIG. 9, it was ascertained that the porosity and bulk density of the silica brick did not change even though chlorine-system waste plastics were charged into the coke oven. Moreover, from the fact that EMPA analysis conducted on silica brick before and after the tests did not detect chlorides from the silica brick it was ascertained that conducting operation with chlorine-system waste plastics added to the raw material does not cause a problem regarding the silica brick of the coke oven.
  • the present inventors conducted a corrosion resistance test by suspending test pieces of SUS (stainless steel) and SS (mild steel) materials in the dry main over a two-month test period. No change was observed in the appearance of the test pieces between before and after the test, while from the fact that, as shown in Table 4, the weight of the test pieces did not change between before and after the test, it was ascertained that the dry main (collecting main) is not affected by addition of chlorine-system waste plastics to the raw material coal.
  • the tar- containing, high-temperature coke-oven gas is cooled, whereby the tar is entained into the ammonia liquor.
  • the tar in the ammonia liquor is separated for use as a byproduct by decantation.
  • the ammonia liquor removed of the tar component is at the first stage stored in a tank, whereafter the ammonia liquor is discharged from the system at the rate of 100-200kg per ton of coke and the remainder of the ammonia liquor is reused for flushing in the coke oven.
  • the flushing with ammonia liquor does cause the chlorine-type gases generated from the coal raw material and the waste plastics during dry distillation to remain in the ammonia liquor as ammonium chloride but water is simultaneously discharged during dry distillation at the rate of 100-200kg (about 5550mol-11000mol) per ton of coke. This is derived from the water contained in coal at about 9% and the water generated in the other reactions at about 3%.
  • the present inventors next conducted a study regarding processing of the ammonium chloride in the ammonia liquor after the chlorine-type gases generated by the waste plastics are captured as ammonium chloride by ammonia liquor flushing. It is a conventional practice to take a portion of the ammonia liquor generated during dry distillation of coal in a coke oven out of the system, subject the ammonia liquor to heating or vapor stripping in an ammonia removing equipment to remove free ammonia by vaporization, and discharge it after effecting activated sludge treatment.
  • the practice has been, particularly in cases where the concentration of the ammonium chloride in the ammonia liquor is high, to subject the ammonia liquor to a pretreatment for freeing ammonia by adding caustic soda to the ammonia liquor before the aforesaid removal of free ammonia by vaporization.
  • the coke, ammonia liquor and COG obtained by dry distillating coal charged into a coke oven were sampled and the Cl concentration of each was investigated.
  • the coke oven measured 430mm in width and 6.5m in height.
  • the total coal dry distillation time was 20hr.
  • the measurement of chlorine concentration of the coal, coke and COG was done by using ion chromatography to measure the Cl ion quantity of the chlorides obtained in accordance with the Testing Method for Cl by the Bomb Combustion Method of JIS K 2541 "Testing Method for Sulfur Component of Petroleum and Petroleum Products" and converting to total Cl amount.
  • the measurement of the chlorine concentration of the ammonia liquor was done by using ion chromatography to measure the Cl ion quantity and converting to total Cl amount. As shown in FIG.
  • the inventors ascertained by the foregoing dry distillation test that when coal was dry distilled alone, 45% of the chlorine component of the coal is transferred to the coke, 54% to the ammonia liquor and 1% to the COG.
  • the chlorine component in the waste plastics was distributed at the rate of about 7% of to the coke, 89% to the ammonia liquor and about 4% to the COG (FIG. 6).
  • the rate of chlorine component residue in the coke was low and almost all of the chlorine component migrated to the ammonia liquor and the COG.
  • the chlorine concentration of the ammonia liquor increased owing to the blending of waste plastics containing chlorine with the coal.
  • FIG. 10 the chlorine concentration of the ammonia liquor increases owing to the blending of waste plastics containing chlorine with the coal.
  • the processing by this method is extremely simple compared with the conventional method of dechlorination of the waste plastics beforehand because it does not require a special dechlorination processing facility or step.
  • plastics having a chlorine content of 3-5wt% are dechlorinated beforehand to a level that does not affect the equipment, i.e., to a chlorine content of 0.5wt% or below, outlays for dechlorination processing equipment and other new facilities are necessary.
  • waste plastics can be effectively recycled by addition of simple equipment for adding the caustic soda needed to make the ammonium chloride in the ammonia liquor after flushing harmless.
  • the dry distillation yield of the waste plastics is about 40% of tar/light oil, about 20% of coke and about 40% of COG.
  • most of the waste plastics thermally decomposed in the coke oven become hydrogen, methane, ethane, propane and other high-calorie reduction-decomposed gases that are contained in the coke- oven gas.
  • they can be reused as by products like tar and light oil and as energy sources such as fuel gas.
  • the remaining carbon component becomes a part of the coke to be reused in a blast furnace. The waste plastics can thus be effectively recycled.
  • Waste plastics discarded as industrial waste are collected from the respective discarding industries separately as ones that, by material property, contain and do not contain chlorine-system plastics and extraneous matter.
  • the waste plastics can be assembled in lots in accordance with the capability of the receiving facility.
  • the waste plastics hauled to the processing facility can be processed beforehand into a condition convenient for charging into a processing facility such as a coke oven or a thermal decomposition furnace. They are, for example, made into pelletized material for a coke oven or thermal decomposition furnace by crushing - extraneous matter removal - and fine chopping (to under around 10mm).
  • Plastics discarded as nonindustrial waste consist plastic rubbish, incombustible rubbish etc. sorted and discarded from households. These are initially collected by local communities. Those assembled in lots at the local community stockyards are transported to the pertinent processing facility by a company contracted to recycle plastic rubbish. In this case, although collection into lots classified by plastic material or extraneous material is impossible, the composition of average sorted plastics is 75% of combustibles consisting mainly of plastics (including 5-10% of chlorine components), 5% of magnetic metals, 2% of aluminum, 8% of glass and other inorganic components (including 5% inorganic components in combustible components), and 10% of water.
  • waste plastics of the nonindustrial waste type When these waste plastics of the nonindustrial waste type are to be charged into a coke oven, thermal decomposition furnace or other such processing facility, they must be sorted beforehand for removal of metals constituting extraneous materials.
  • the collected waste plastics are subjected to tearing of plastic bags - magnetic sorting - extraneous material removal (of nonmagnetic material).
  • waste plastics of the nonindustrial waste type are collected as films, foamed bodies and powders, so that the charge material obtained by merely comminuting them to a prescribed particle size would have a small bulk density and a large bulk. As it would also contain excessive powder, it might sometimes be difficult to charge.
  • plastic with a small bulk density and a large bulk is very troublesome to handle since it is liable to ignite in the vicinity of a high-temperature coke oven or thermal decomposition furnace.
  • the chlorine-containing plastics are heated to a temperature of 80°C-190°C, compressed in this state and then recooled, thereby effecting volume-reduction and hardening.
  • the nonindustrial waste plastic After passing through these operations, the nonindustrial waste plastic obtains a condition convenient for charging in a coke oven or a thermal decomposition furnace, e.g., has an ash content of not more than 10%, a chlorine component of not greater than 3.0%, a particle size of 10-70mm, a lower calorific value of not less than 5000Kcal/kg, and heavy metal of not greater than 1%.
  • the size of the volume-reduced and hardened material the design can be made appropriately in light of transportability and, in the case of adopting a coke oven, mixability with coal, coke strength when dry distilled together with coal, danger of ignition and the like. Generally, however, around 5-lOmm is appropriate.
  • a conventionally used resin kneader, drum-type heater or the like there can be adopted.
  • the furnace used in the present invention to thermally decompose the chlorine-containing plastics there can be adopted a furnace having a furnace wall structure that can be heated to 600°C and higher, that possesses corrosion resistance against chlorine-type gases, e.g., one having a refractory wall constituted of silica brick, chamotte brick or the like, and it suffices to equip this furnace with a unit for dissolving the ammonia of the generated gas in water and flushing the waste gas therewith.
  • it can be a coke oven (FIG. 2) or, otherwise, a dedicated thermal decomposition furnace provided alongside a coke oven.
  • the thermal decomposition gas generated by the thermal decomposition furnace can be led to the ascension pipes of the coke oven and ammonia liquor be used to incorporate chlorine-type gases into the ammonia liquor as ammonium chloride.
  • the generated hydrogen chloride gas and ammonia gas pass through an oven-top space 4 above the charged material in the coke oven chamber 2 and then through an ascension pipe 5 provided above the coke oven chamber to a bend pipe 6.
  • the gas temperature is around 800°C at the oven-top space 4 and about 700 °C at the ascension pipe section.
  • the material of the ascension pipes is generally cast iron.
  • the design should preferably take into account corrosion of the pipe material up to the dry main, where ammonia gas is water- sprayed (flushing). Also regarding the shield plates and knife edges of the coke oven, although in the inventors' studies no particular problem was observed concerning corrosivity even when ordinary materials were used, in consideration of long-term corrosion resistance the material should preferably be changed as required, e.g. to two-phase stainless steel or incoloy.
  • Methods usable for charging the waste plastics into the coke oven or the thermal decomposition furnace installed alongside include the method of making additions at the oven- or top space of the coke chamber (e.g., JP-A- 9-157834), the method of making additions at the bottom of the coke oven chambers (e.g., JP-A-9-132782 ) , and the method of charging after premixing with coal (e.g., JP-A- 6-228565).
  • the preferable method is to effect gas-stream conveyance to the oven-top space using an inert gas and then to use a storage hopper with fixed amount dispensing capability to dump the waste plastics into the specified coke oven chambers together with the inert gas. Further, in order to avoid the problems of thermal decomposition gas blowout and atmospheric air intake, charging of the waste plastics is preferable conducted in a state sealed off from the atmosphere. Specifically, there can be adopted the method of charging into the space above the coke oven chambers taught in the applicant's JP-A-4-41588.
  • some of the multiple coke oven chambers can be used as dedicated chambers for recycle-processing of waste plastics.
  • this is a method of designating several chambers of a coke oven composed of more than 100 coke oven chambers exclusively for heat treatment of waste plastics, using circulated ammonia liquor to flush both the chlorine-type gases generated by thermal decomposition in these and the coke-oven gas, capturing the chlorine- type gases in the coke-oven gas in the ammonia liquor as ammonium chloride, and then adding a strong base to free ammonia and make the chlorine component harmless.
  • This method can be carried out with equipment that is capable of using an aqueous ammonium solution like the flushing ammonia liquor of a coke oven in common at all coke oven chambers.
  • This method uses some of the coke oven chambers as dedicated chambers for thermal decomposition of chlorine-containing plastics and, therefore, unlike in the case of dry distillating chlorine-containing plastics and coal together in the same coke oven chamber, it imposes no limit from the point of coke quality degradation on the amount of waste plastics charged and enables the temperature of the dedicated coke oven chambers to be appropriately set within a broad range extending from 400- 1300°C.
  • chlorine-containing waste plastics can be processed in an amount chemically equivalent to the ammonia generated by the coal and, therefore, chlorine-containing waste plastics can be dry distilled and thermally decomposed in the coke oven up to a maximum of 26wt% of the charged coal.
  • specific gravity of coal is about twice that of plastic, even if 34 chambers (34%) of a coke oven having 100 chambers are defined as chambers exclusively for thermal decomposition of chlorine-containing plastics and the remaining 66 chambers (66%) are used as coal dry distillation chambers, it is theoretically possible to supply enough ammonia for conversion of all chlorine discharged from the chlorine- containing waste plastics to ammonium chloride.
  • up to a limit of 5 chambers (5%) to 10 chambers (10%) should preferably be designated as coke oven chambers exclusively for thermal decomposition of chlorine-containing plastics.
  • the method explained in the following can be adopted for measuring the chlorine content of waste plastics. Repeatedly apply the quartering method to 10kg of waste plastics comminuted to 10-20mm until finally subdividing to typical samples of 20g each. Freeze-crush the samples into powder.
  • As the qualitative analysis method use X-ray fluorescence analysis to obtain percent-order analysis results for the powders .
  • As the quantitative analysis method use ion chromatography to measure the Cl ion quantity of the chlorides obtained in accordance with the Testing Method for Cl by the Bomb Combustion Method of JIS K 2541 "Testing Method for Sulfur Component of Petroleum and Petroleum Products" and convert to total Cl amounts. Based on the results, define the chlorine content as the average value.
  • the percentage of the total amount of charged raw material accounted for by the chlorine-containing waste plastics differs between the case of charging the chlorine-containing waste plastics after blending them with the raw material coal beforehand and the case of not blending them beforehand.
  • chlorine-containing waste plastics classified/recovered from general households contains 5-10wt% of chlorine, it has a chlorine content of approximately 2% after passing through ensuing winnowing and other waste plastic dry sorting.
  • the chlorine content of the waste plastics can be made lower and a larger amount of chlorine- containing plastics can be processed than in the case of winnowing and other dry sorting but, conversely, the yield of the plastic sorting decreases.
  • the coal charged together with the chlorine- containing plastics need only be one that generates coke- oven gas containing ammonia and water. Selection of type of coal as in an ordinary coking operation is unnecessary.
  • the percentage of total charged raw material accounted for by the chlorine-containing waste plastics is set in the range of 0.05-26wt%.
  • the percentage of total charged raw material accounted for by chlorine-containing waste plastics exceeds 26wt%, the amount of raw material coal is insufficient for supplying the amount of ammonia needed to capture the chlorine-type gases generated from the chlorine-containing plastics in the ammonia liquor as ammonium chloride.
  • the upper limit thereof is therefore set at 26wt%. If the percentage of chlorine-containing waste plastics becomes less than 0.05wt%, the practical merit as a process for recycling waste plastics with a coke oven is lost.
  • the percentage of total charged raw material accounted for by the chlorine-containing waste plastics is set in the range of 0.05-lwt%.
  • the percentage of chlorine-containing waste plastics is less than 0.5wt%, the practical merit as a process for recycling waste plastics is too small.
  • it exceeds lwt% the coke strength sharply decreases.
  • FIG. 3 is shows the relationship between amount of added waste plastics and coke strength.
  • ammonia liquor is present for capturing the chlorine-type gases generated from the waste plastics.
  • an amount of coal is used that generates ammonia at 1.1 to 2 times the molar amount of chlorine in the generated chlorine-type gases.
  • the lower limit of the amount of ammonia generated by the coal is preferably set at 1.1 times in order to thoroughly capture the chlorine component as ammonium chloride.
  • the upper limit is set at 2 times the molar amount of chlorine in the chlorine-type gases.
  • the amount of coal needed to process one ton of chlorine-containing waste plastics with a chlorine content of 2wt% is 4. It to 7.5t.
  • the amount of waste plastics added relative to the coal is regulated by the following method. After the waste plastics have been placed in the waste plastic hopper, a feeder is used to regulate the amount of waste plastics dispensed from the hopper per unit time, thereby regulating the amount added to the coal.
  • a feeder is used to regulate the amount of waste plastics dispensed from the hopper per unit time, thereby regulating the amount added to the coal.
  • the grade of coal blended as the raw material coal in this case is therefore preferably selected so as to compensate for the decrease in coke strength owing to the charging of waste plastics.
  • the raw material coal and the waste plastics are charged into the coke oven and dry distilled without being blended in advance, however, degradation of coke quality can be avoided even if the amount of charged waste plastics exceeds lwt% of the raw material coal.
  • the raw material coal therefore need not be specially selected as a grade of blending coal to compensate for decline in coal strength by waste plastic charging.
  • Coal can generally be classified into coking coal suitable for production of blast furnace coke and noncoking coal not appropriate for this purpose. In actual coke oven operation, coking coal and noncoking coal are used at an arbitrary blending ratio to obtain the desired coke quality.
  • Noncoking coal as termed here is generally coal having a maximum fluidity index of lOddpm as determined by a fluidity test conducted by the Gieseler plastometer method prescribed by JIS M 8801 or having a vitrinite mean reflectance of not greater than 0.8.
  • coking coals usable for strength compensation can be adopted, for example, Goonyella coal, North Goonyella coal, Saraji coal, Blue Creek coal, Luscar coal, Riverside coal, Elkview coal, Line Creek coal and the like.
  • the temperature in the case of dry distillating waste plastics in a coke oven chamber can be the same as in ordinary coke oven operation.
  • the optimum temperature when dry distillating coal in a coke oven is ordinarily 1300 °C. This is because polyvinyl chloride, polyvinylidene chloride and the like usually undergo thermal decomposition at around 250 °C, gasify at about 400 °C and totally decompose at 1300 °C.
  • the dry distillation temperature and dry distillation pattern can be can be implemented under the operating conditions during ordinary coal dry distillation.
  • Methods available for capturing the chlorine-type gases generated by thermal decomposition of waste plastics as ammonium chloride include, in addition to using ammonia liquor (ammonia and water generated by coal dry distillation) circulated for use in the coke oven as described in the foregoing, that of using a gas or aqueous solution containing ammonia produced by another method in an amount chemically equivalent to the chlorine and bringing it into contact with the chlorine.
  • ammonia liquor ammonia and water generated by coal dry distillation
  • the sublimation point of ammonium chloride is 337.8°C and a high temperature state exits after thermal decomposition of the waste plastics in the coke oven or the thermal decomposition furnace.
  • aqueous ammonia solution is therefore particularly preferable.
  • ammonia gas or aqueous ammonia is used to capture the chlorine-type gases generated by thermal decomposition of the waste plastics as ammonium chloride, the high processing cost makes it preferable to use, for example, the aqueous ammonia (ammonia liquor) generated during coal dry distillation in a coke oven or the like.
  • the ammonium chloride generated by contact between the chlorine-type gases generated by the waste plastics and ammonia is soluble in water.
  • the temperature in the space at the top of the coke oven chamber is about 800 °C and the hydrogen chloride gas and other chlorine-type gases generated by the waste plastics and the ammonia gas pass through the oven-top space and then through the ascension pipes provided above the coke oven chambers to bend sections of the ascension pipes.
  • the gas temperature at the ascension pipe sections is about 700 °C.
  • the method conventionally used in coke ovens can be adopted as the flushing method.
  • cast iron is generally used as the material of the ascension pipes
  • the pipe material specifications up to the dry main where ammonia gas is water-sprayed (flushing) can, depending on the circumstances, be altered taking corrosion into account.
  • the waste plastics can be thermally decomposed using a thermal decomposition furnace instead of a coke oven. This can be achieved by installing a unit for contacting the thermal decomposition gas discharged from the thermal decomposition furnace and the ammonia-containing gas and a unit for adding a strong base to the water containing the ammonium chloride alongside the thermal decomposition furnace.
  • the method can be adopted of installing the thermal decomposition furnace alongside the coke oven and leading the thermal decomposition gas containing chlorine-type gases after thermal decomposition of the waste plastics in the thermal decomposition furnace to the ascension pipe sections of the coke oven.
  • a strong base e.g., sodium hydroxide (caustic soda 16) is added to the ammonia liquor or aqueous ammonia containing ammonium chloride extracted to the exterior of the coke oven or thermal decomposition furnace system (see 16 in FIG. 1).
  • the ammonium chloride in the ammonia liquor or aqueous ammonia reacts with the sodium hydroxide to become sodium chloride and ammonia.
  • the amount of sodium hydroxide added is preferably the chemical equivalent of the ammonium chloride or a slightly larger amount.
  • Some other strong base such as potassium hydroxide can be adopted in place of sodium hydroxide.
  • the nitrogen content of the ammonia liquor is controlled by the following method.
  • Ammonium chloride in the ammonia liquor is converted to ammonia and sodium chloride by adding caustic soda to the ammonia liquor, whereafter nitrogen is removed from the ammonia liquor by vaporizing and removing ammonia in an ammonia remover.
  • the rate of caustic soda addition (mol ratio) necessary for the ammonium chloride concentration of the ammonia liquor is calculated beforehand, as shown by the example of
  • caustic soda is added based on the measured value of the ammonium chloride concentration of the ammonia liquor and the calculated caustic soda addition rate.
  • the total nitrogen content before and after caustic soda addition was measured several times a day and operation was conducted while confirming that the total nitrogen content stayed at or below a reference value.
  • the caustic soda was added through a pipe 20 connected to the suction side of an ammonia liquor payout pump 21 installed on the outlet side of a source ammonia liquor tank 15.
  • the ammonium chloride becomes sodium chloride and ammonia (see 17 in FIG. 1).
  • the ammonia 17 is separated and recovered in an ammonia remover 9 and put to effective use, while the remainder is discharged into seawater after being subjected to activated sludge treatment.
  • the ammonia remover can be one of a conventional type such as the vapor stripping type.
  • Measurement of the total nitrogen concentration of the effluent was conducted in accordance with the summing method described in JIS K 0102 and ultraviolet absorptiometry.
  • the sample is added with sodium hydroxide and distilled, ammonia produced by decomposition of ammonia ions and some of the organic nitrogen compounds are removed, Devarda's alloy is added to reduce nitrous acid ions and nitric acid ions to ammonia, the ammonia is separated by distillation, and the amount of nitrogen is determined by indophenol blue absorptiometry.
  • a sample is added with copper sulfate, potassium sulfate and sulfuric acid and heated to effect decomposition and change organic nitrogen compounds into ammonium ions, followed by distillation as alkaline to distill and separate ammonium ions contained in the sample together therewith, and determination of nitrogen amount by indophenol blue absorptiometry.
  • the method calculates total nitrogen concentration by combining this amount with a nitrogen amount corresponding to the nitrous acid ions and nitric acid ions found earlier.
  • total nitrogen amount is analyzed by the following method.
  • the sample is added with alkaline solution of potassium peroxodisulfate and heated to about 120 °C to convert nitrogen compounds to nitric acid ions and decompose organic substances. After the pH of this solution has been adjusted to 2-3, determination is effected by absorptiometric measurement of 220nm wavelength of the nitric acid ions. Since the organic substances in the sample are readily decomposed and the quantity is small, this method is simpler than the foregoing summing method. It is also effective to adjust the amount of added caustic soda according to periodic fluctuations in the so- measured effluent nitrogen concentration.
  • the tar component contained in the ammonia liquor after flushing is separated from the water component by decantation (see 8 in FIG. 1 ) .
  • the tar component after separation includes around 2-3% of residual ammonia liquor, it includes ammonium chloride, but normally at a level that is not a problem.
  • the chlorine component concentration of the tar is preferably further dewatered using a centrifuge or the like to maintain the same level as when waste plastics are not added.
  • Waste plastics containing chlorine-system resins were comminuted to about 10mm and volume-reduced using a screw kneader.
  • the volume-reduction temperature was about 120 °C owing to screw friction heating. What was obtained by cutting these to a diameter of about 10mm and air-cooling them on a conveyor belt was mixed in advance with coal at the blending ratios shown in Figure 5 and charged into the coke oven chambers of a coke oven battery having 100 coke oven chambers. Charging into the coke oven was from the top of the coke oven by the same method as for conventional coal charging.
  • the dry distillation pattern adopted was the same as that for conventional coke production.
  • the total dry distillation time was 20hr.
  • Example 6-9 the percentage of coking coal contained in the blended coal was increased over that in Examples 1-5 in order to maintain the coke strength.
  • Example 9 dry distillation was conducted with only waste plastics charged into 5 of the 100 coke oven chambers and the same blended coal as in Examples 1-3 charged into the remaining 95 chambers.
  • the strength of the coke forced out of the coke oven chambers after dry distillation was evaluated as O when the drum strength of the coke determined in conformity with JIS K 2151 (+15mm after 150 revolutions) was 84 or greater and was evaluated as X when less than 84.
  • the chlorine concentration of the light oil was evaluated as O when lOppm or less and as X when greater than lOppm.
  • the capture ratio by flushing was evaluated as O when 90% or greater and as X when less than 90%.
  • the waste water removed of ammonia by addition of caustic soda and vapor stripping was diluted 40 fold and an evaluation of O was made when the nitrogen concentration of the diluted effluent was 20mg/l or less and an evaluation of X was made when it was greater than 20mg/l.
  • FIG. 14 is shows the effect on coke productivity.
  • the coking time with l-2wt% addition of waste plastics was substantially the same as in the case of coal only and the addition of waste plastics had substantially no effect on dry distillation time or productivity.
  • the bulk density of the waste plastics was small, however, when they were added to the coal, the bulk density decreased at the time of charging into the coke oven.
  • the addition of waste plastics lowered the amount of charged raw material coal, the coke productivity declined, but the effect thereof was slight.
  • FIG. 15 shows the charged coal amount scatter when waste plastics were added. Addition of waste plastics caused no increase in charged coal amount scatter and did not affect the charging operation.
  • FIG. 16 shows gas pressure in the coal when waste plastics were added. No change in coal internal gas pressure owing to waste plastic addition was observed.
  • FIG. 17 shows carbon adhesion when waste plastics were added. No increase in amount of adhering carbon owing to waste plastics addition was observed.
  • This invention uses the ammonia gas contained in the coal gas etc. generated during dry distillation of coal to convert to ammonium chloride the hydrogen chloride and other chlorine-type gases generated by thermal decomposition of charged raw material including chlorine- containing resin, chlorine-containing organic compound, or waste plastic containing the same, dissolves the generated ammonium chloride in ammonia liquor and, after discharge, decomposes it with sodium hydroxide to remove nitrogen, so that the charged raw material of chlorine-containing resin, chlorine-containing organic compound, or waste plastic containing the same can further be thermally decomposed without increasing the nitrogen content of the discharged ammonia liquor, thereby enabling reuse as gas and reuse as coke raw material.

Abstract

Un procédé de traitement de résines contenant du chlore et de composés organiques contenant du chlore consiste à décomposer thermiquement les résines contenant du chlore, les composés organiques contenant du chlore ou des matières plastiques résiduelles les contenant, à mettre en contact le gaz de décomposition thermique produit contenant des gaz de type chlore et un gaz ou un liquide contenant de l'ammoniac, et à mettre le constituant de chlore du gaz de décomposition thermique dans de l'eau sous forme de chlorure d'ammonium, puis à ajouter une base forte afin de transformer le constituant de chlore en un sel basique fort.
PCT/JP1999/004052 1998-07-29 1999-07-28 Procede de traitement de composes organiques contenant du chlore WO2000006668A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU49291/99A AU4929199A (en) 1998-07-29 1999-07-28 Method for processing chlorine-containing organic compounds
CA002338611A CA2338611C (fr) 1998-07-29 1999-07-28 Methode pour effectuer en parralele du charbon cokefiable et pour traiter de la resine contenant du chlore, composes organiques contenant du chlore ou de dechet de plastique contenant du chlore
US09/744,631 US6329496B1 (en) 1998-07-29 1999-07-28 Method for processing chlorine-containing organic compounds
DE69930519T DE69930519T2 (de) 1998-07-29 1999-07-28 Verfahren zur behandlung von chlor enthaltenden organischen verbindungen
EP99933136A EP1114123B1 (fr) 1998-07-29 1999-07-28 Procede de traitement de composes organiques contenant du chlore

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP21381798 1998-07-29
JP10/213817 1998-07-29
JP1798999 1999-06-25
JP11/179899 1999-06-25

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WO2000006668A1 true WO2000006668A1 (fr) 2000-02-10

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6956016B2 (en) 2001-05-14 2005-10-18 The Procter & Gamble Company Cleaning product
EP1679168A2 (fr) * 2003-10-21 2006-07-12 Nippon Steel Corporation Procede de recyclage de dechets plastiques et procede de moulage

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3531514C1 (en) * 1985-09-04 1987-04-09 Daimler Benz Ag Process for the decomposition of plastic or paint residues by pyrolysis in a fluidized bed
DE4012397C1 (en) * 1990-04-19 1992-02-20 Sinn, Hansjoerg, Prof. Dr., 2000 Norderstedt, De Halogen hydride removal - by adding ammonia to pyrolysis gas in an agitated bed of pyrolysis reactor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3531514C1 (en) * 1985-09-04 1987-04-09 Daimler Benz Ag Process for the decomposition of plastic or paint residues by pyrolysis in a fluidized bed
DE4012397C1 (en) * 1990-04-19 1992-02-20 Sinn, Hansjoerg, Prof. Dr., 2000 Norderstedt, De Halogen hydride removal - by adding ammonia to pyrolysis gas in an agitated bed of pyrolysis reactor

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6956016B2 (en) 2001-05-14 2005-10-18 The Procter & Gamble Company Cleaning product
US7078462B2 (en) 2001-05-14 2006-07-18 The Procter & Gamble Company Cleaning product
EP1679168A2 (fr) * 2003-10-21 2006-07-12 Nippon Steel Corporation Procede de recyclage de dechets plastiques et procede de moulage
EP1679168A4 (fr) * 2003-10-21 2009-09-23 Nippon Steel Corp Procede de recyclage de dechets plastiques et procede de moulage
US7695669B2 (en) 2003-10-21 2010-04-13 Nippon Steel Corporation Method of reutilization and method of shaping of waste plastic

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